Cd(II) and Cu(II) coordination polymers based on a multidentate N-donor ligand: syntheses,crystal structures,optical band gaps,and photoluminescence

Four Cd(II)- and Cu(II)-containing coordination polymers (CPs) based on a multidentate N-donor ligand and varied dicarboxylate anions, [Cd(3,3′-tmbpt)(p-bdc)]·2.5H₂O (1), [Cd(3,3′-tmbpt)(m-bdc)]·2H₂O (2), [Cu(3,3′-tmbpt)(m-bdc)]·H₂O (3), and [Cu(3,3′-tmbpt)(p-bdc)]·2H₂O (4), where 3,3′-tmbpt = 1 ? ((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole, p-H₂bdc = 1,4-benzenedicarboxylic acid, and m-H₂bdc = 1,3-benzenedicarboxylic acid, have been prepared hydrothermally. The structures of the compounds were determined by single-crystal X-ray diffraction analyses and further characterized by infrared spectra and elemental analyses. Compound 1 exhibits a 3-D twofold interpenetrating framework with a 6⁵·8 CdSO₄ topology. Compound 2 is a 2-D layer containing meso-helical chains with a 4⁴·6² sql topology. Compound 3 shows a 1-D → 3-D interdigitated architecture while 4 displays a 2-D → 3-D interdigitated architecture. The structural differences of the compounds indicate that the dicarboxylate anions and the central metal ions play important roles in the resulting structures of CPs. Optical band gaps and solid-state photoluminescent properties have also been studied.     

Four Zn(II)/Cd(II) coordination polymers derived from isomeric benzenedicarboxylates and 1,6-bis(triazol)hexane ligand: synthesis,crystal structure,and luminescent properties

Four coordination polymers, [Zn(o-bdc)(bth)_0.5(H₂O)] _n (1), [Cd(o-bdc)(bth)_0.5(H₂O)] _n (2), [Zn(m-bdc)(bth)] _n (3), and [Cd(p-bdc)(bth)?·?(H₂O)₂] _n (4) (where o-bdc?=?1,2-benzenedicarboxylate, m-bdc?=?1,3-benzenedicarboxylate, p-bdc?=?1,4-benzenedicarboxylate, and bth?=?1,6-bis(triazol)hexane), have been hydrothermally synthesized and structurally characterized. Both 1 and 2 are isostructural, featuring two binodal architectures: (6³)(6⁵·8) topology in terms of o-bdc and Zn^II/Cd^II as three- and four-connected nodes. Complex 3 shows a 2-D (4,4) network with the Zn?···?Zn?···?Zn angle of 57.84°, whereas 4 exhibits planar 2-D (4,4) network. These 2-D networks of 3 and 4 are extended by supramolecular interactions, such as CH?···?π/π–π stacking and hydrogen-bonding into 3-D architecture. A structural comparison of these complexes demonstrates that the dicarboxylate building blocks with different dispositions of the carboxyl site play a key role in governing the coordination motifs as well as 3-D supramolecular lattices. Solid-state properties such as photoluminescence and thermal stabilities of 1–4 have also been studied.     

Two independent, 1-D metal–organic nanotubes based on rings or helical chain units

Three coordination polymers {[Mn(bte)(NO₂-1,3-bdc)(H₂O)]·H₂O}_n (1), {[Mn(btp)(NO₂-1,3-bdc)(H₂O)]·2H₂O}_n (2), and {[Mn(btb)(NO₂-1,3-bdc)(H₂O)]·H₂O}_n (3) (bte, 1,2-bis(1,2,4-triazol-1-yl)ethane; btp, 1,3-bis(1,2,4-triazol-1-yl)propane; btb, 1,4-bis(1,2,4-triazol-1-yl)butane, NO₂-1,3- H₂bdc, 5-nitroisophthalic acid) were synthesized by combination of bte, btp, and btb, conformationally flexible ligands with different spacer lengths, and the rigid [NO₂-1,3-bdc]^2?. In 1, two [NO₂-1,3-bdc]^2? anions link adjacent [Mn₂(bte)₂] rings to give an independent, 1-D metal–organic nanotube (MONT). The structure of 2 is an undulating 2-D (4,4) network. In 3, the combination of a [Mn(btb)]_n single helical chain and two [Mn(NO₂-1,3-bdc)]_n linear chains assemble an intriguing independent, 1-D MONT. An interesting structural feature of 1 and 3 is that the nitro groups of each 1-D MONT interpenetrate into two adjacent 1-D MONTs to form a 1-D → 2-D interdigitated array. 3-D architectures in 1 and 3 are assembled via hydrogen bond interactions. The luminescent properties and thermal stabilities of 1, 2, and 3 were investigated.     

Two manganese(II) complexes constructed from 2-(3-pyridyl)-imidazo[4,5-f] 1,10-phenanthroline and organic dicarboxylates: syntheses,crystal structures,and luminescence

In this study, two new Mn(II) complexes consisting of a phenanthroline derivative and organic acid ligands, [Mn(3-PIP)(1,3-bdc)] _n (1) and [Mn(3-PIP)₂(1,4-bdc)] _n (2) (3-PIP?=?2-(3-pyridyl)-imidazo[4,5-f]?1,10-phenanthroline, 1,3-H₂bdc?=?benzene-1,3-dicarboxylic acid, 1,4-H₂bdc?=?benzene-1,4-dicarboxylic acid), have been synthesized via hydrothermal reaction and characterized by Fourier transform infrared (FT-IR) spectra, elemental analyses, and single-crystal X-ray diffraction. Complex 1 is a one-dimensional (1-D) twisted double chain bridged by 1,3-bdc. The 3-PIP ligands in a parallel fashion are alternately attached to both sides of the 1-D double chain. Complex 2 exhibits a 1-D zigzag chain, to which pairs of crossed 3-PIP ligands are alternately attached. The two complexes are further extended into three-dimensional (3-D) supramolecular structures by hydrogen-bonding and π–π stacking interactions. The N-donor ligands with an extended π-system play a crucial role in formation and stabilization of the final supramolecular frameworks. Thermal properties of 1 and 2 and fluorescence of 2 are investigated in the solid state.     

Coordination Frameworks based on 3,5‐Bis(imidazole‐1‐yl)­pyridine and Aromatic Dicarboxylate Ligands: Synthesis,Crystal Structures,and Photoluminescent Properties

Three metal coordination polymers [Zn(bdc)(L)(H₂O)]_n ( 1 ), [Co(pta)(L)(H₂O)₂]_n ( 2 ), and [Cd(tda)(L)(H₂O)]_n ( 3 ) [H₂bdc = 1,2‐benzene dicarboxylate acid, H₂pta = terephthalic acid, H₂tda = 2,5‐thiophenedicarboxylic acid, L = 3,5‐bis(imidazole‐1‐yl)pyridine] were synthesized and structurally characterized by IR spectroscopy, elemental analysis, X‐ray powder diffraction, and X‐ray single crystal diffraction. Complex 1 shows a three‐dimensional (3D) structure with cco topology with the symbol 6⁵ · 8, whereas complex 2 features a 3D structure with cds topology with the symbol 6⁵ · 8. Complex 3 has a 2D network constructed by the cadmium atoms bridged through the ligands tda and L. Their X‐ray powder diffraction patterns were compared with the simulated ones. Moreover, their luminescent properties were investigated in the solid state at room temperature, and the thermogravimetric analyses were carried out to study the thermal stability of the 3D networks.     

Two 3d‐4f Heterometallic Coordination Polymers of Macrocyclic Oxamide with Benzotriazole‐5‐carboxylate Co‐ligand: Syntheses,Crystal Structures and Magnetic Properties

Two heterometallic 3d–4f coordination polymers, [Gd(CuL)₂(Hbtca)(btca)(H₂O)] · 2H₂O ( 1 ) and [Er(CuL)₂(Hbtca)(btca)(H₂O)] · H₂O · CH₃OH ( 2 ) (CuL, H₂L = 2,3‐dioxo‐5,6,14,15‐dibenzo‐1,4,8,12‐tetraazacyclo‐pentadeca‐7,13‐dien; H₂btca = benzotriazole‐5‐carboxylic acid) were synthesized by solvothermal methods and characterized by single‐crystal X‐ray diffraction. Complexes 1 and 2 exhibit a double‐strand meso‐helical chain structures formed by [Ln^IIICu^II₂] (Ln^III = Gd, Er) units by oxamide and benzotriazole‐5‐carboxylate bridges. They are isomorphic except that one free water molecule of 1 is replaced by a methanol molecule. All 1D chains are further interlinked by hydrogen bonds resulting in a 3D supramolecular architecture. The magnetic properties of the compound 1 and 2 are also discussed.     

Synthesis,Structures, and Properties of two Helical Structures from Rigid Carboxylate Ligand and Flexible N‐Bridging Ligands

Two novel coordination polymers based on mixed ligands, [Zn(dpb)(bdc)(H₂O)]_n ( 1 ) and [Cd(dpb)(bbdc)(H₂O)(DMF)]_n ( 2 ) [dpb = 1, 4‐bis(pyridin‐3‐ylmethoxy)benzene, H₂bdc = 1, 4‐benzenedicarboxylate, H₂bbdc = 4, 4′‐dibenzenedicarboxylate], were synthesized under hydrothermal conditions. Compound 1 forms meso‐helical chain and shows three fold interpenetrating architecture with 4‐connected net {6 6} diamond topology. Compound 2 is a left‐ and right‐handed helical layer, which are interacted by π–π stacking interactions to construct a 3D framework. The luminescent properties of the compounds are discussed.     

Organic carboxylate anions effect on the structures of a series of Mn(II) complexes based on 2-phenylimidazo[4,5-f]1,10-phenanthroline ligand

In our efforts to tune the structures of Mn(II) complexes by selection of organic carboxylic acid ligands, six new complexes [Mn(PIP)₂Cl₂] (1), [Mn(PIP)₂(4,4′-bpdc)(H₂O)]·2H₂O (2), [Mn(PIP)₂(1,4-bdc)] (3), [Mn(PIP)(1,3-bdc)] (4), [Mn(PIP)₂(2,6-napdc)]·H₂O (5), and [Mn(PIP)(1,4-napdc)]·H₂O (6) were obtained, where PIP=2-phenylimidazo[4,5-f]1,10-phenanthroline, 4,4′-H₂bpdc=biphenyl-4,4′-dicarboxylic acid, 1,4-H₂bdc=benzene-1,4-dicarboxylic acid, 1,3-H₂bdc=benzene-1,3-dicarboxylic acid, 2,6-H₂napdc=2,6-naphthalenedicarboxylic acid, 1,4-H₂napdc=1,4-naphthalenedicarboxylic acid. All complexes have been structurally characterized by IR, elemental analyses, and single crystal X-ray diffraction. Structural analyses show that complexes 1 and 2 possess mononuclear structures, complexes 3, 4, and 5 feature chain structures, and complex 6 exhibits a 2D (4,4) network. The structural difference of 1–6 indicates that organic carboxylate anions play important roles in the formation of such coordination architectures. Furthermore, the thermal properties of complexes 1–6 and the magnetic property of 4 have been investigated.     

Syntheses,Structures and Properties of Four New Transitional Metal Complexes Based on Benzotriazole‐5‐carboxylic Acid

Four new complexes, [Zn(btca)(2,2′‐bpy)] ( 1 ), [Mn(btca)(2,2′‐bpy)] ( 2 ), [Co(btca)(phen)] ( 3 ), and [Cu(btca)(phen)] ( 4 ), (H₂btca=benzotriazole‐5‐carboxylic acid, 2,2′‐bpy=2,2′‐bipyridine, phen=1,10‐phenanthroline), were successfully synthesized and characterized by elemental analysis, single crystal X‐ray diffraction, and IR spectroscopy. Complexes 1 – 4 crystallize in the orthorhombic system with space group of Pbca and show similar 2D layers, which are interlinked to supramolecular networks by π‐π stacking interactions. Furthermore, TGA curves show that complexes 1 – 4 have good thermal stability. Solid‐state fluorescent property of complex 1 was also investigated at room temperature.     

Uranyl-containing heterometallic coordination polymers based on 4-(4’-carboxyphenyl)-1,2,4-triazole ligand: structure regulation through subtle changes of the secondary metal centers

Abstract

Three uranyl-containing coordination polymers, Cd(UO₂)₂(cpt)₄(bdc)(H₂O)₂ (1), Zn(UO₂)₂(cpt)₄(bdc)(H₂O)₂ (2) and UO₂(OH)(cpt) (3) (Hcpt =4-(4’-carboxyphenyl)-1,2,4triazole, H₂bdc =1,4-benzenedicarboxylic acid), have been synthesized under hydrothermal conditions by employing a bifunctional ligand (Hcpt) with both O-donors and N-donors. Compound 1 represents a 3-D framework with the point symbol of (6²·8⁴)(6²·8)₂ by the intersection of two sets of 1-D [Cd₂(UO₂)₂(cpt)₄(bdc)]_n loop chains extended along different directions. Compound 2 exhibits a 2-nodal (3,4)-connected 2-D network with the point symbol (4·6²)₂(4²·6²·8²). Compound 3 shows a 2-D network by the assembly of uranyl dimers and the cpt^- anions. Although 1 and 2 have similar chemical formulas and the same coordination modes of ligands and metal centers, they possess totally different molecular frameworks, derived from the different radii of the secondary metal centers, Cd(II) and Zn(II). In addition, the optimal synthesis condition, thermal stability, luminescent properties, and IR spectra of 1 and 2 were also investigated.     

Four silver-containing coordination polymers based on bis(imidazole) ligands

Four coordination polymers, [Ag(L¹)](m-Hbdc) (1), [Ag(L¹)]₂(p-bdc)?·?8H₂O (2), [Ag(Hbtc)(L¹)][Ag(L¹)]?·?2H₂O (3) and [Ag₂(L²)₂](OH-bdc)₂?·?4H₂O (4), where L¹?=?1,1′-(1,4-butanediyl)bis(imidazole), L²?=?1,2-bis(imidazol-1-ylmethyl)benzene, m-H₂bdc?=?1,3-benzenedicarboxylic acid, p-H₂bdc?=?1,4-benzenedicarboxylic acid, H₃btc?=?1,3,5-benzenetricarboxylic acid, and OH–H₂bdc?=?5-hydroxisophthalic acid, were synthesized under hydrothermal conditions. Compound 1 contains a–Ag-L¹–Ag-L¹–chain and a hydrogen-bonding interaction induced–(m-Hbdc)-(m-Hbdc)–chain. Compound 2 consists of two independent–Ag-L¹–Ag-L¹–chains. P-bdc anions are not coordinated. Hydrogen bonds form a 3D supramolecular structure. A novel (H₂O)₁₆ cluster is formed by lattice water molecules in 2. Compound 3 contains a–Ag-L¹–Ag-L¹–and a–Ag(Hbtc)-L¹–Ag(Hbtc)-L¹–chain. The packing diagram shows a 2D criss-cross supramolecular structure, with?π?···?π?and C–H ···?π?interactions stabilizing the framework. Compound 4 contains a [Ag₂(L²)₂]²⁺ dimer with hydrogen-bonding,?π?··· π, and Ag ··· O interactions forming a 3D supramolecular framework. The luminescent properties for these compounds in the solid state are discussed.     

A series of metal-organic frameworks based on 9,10-bis(imidazol-1-ylmethyl)anthracene and structurally related aromatic dicarboxylates: Syntheses, structures, and photoluminescence

A series of new metal-organic frameworks (MOFs) based on 9,10-bis(imidazol-1-ylmethyl)anthracene and four structurally related aromatic dicarboxylates, namely, [Cd(L)(o-bdc)]·1.25H₂O (1), [Cd(L)(pydc)] (2), [Zn(L)(pydc)] (3), [Cd₃(L)₂(m-bdc)₃] (4) and [Cd(L)(p-bdc)]·2H₂O (5) (L = 9,10-bis(imidazol-1-ylmethyl)anthracene, o-H₂bdc = 1,2-benzenedicarboxylic acid, H₂pydc = 2,3-pyridinedicarboxylic acid, m-H₂bdc = 1,3-benzenedicarboxylic acid, p-H₂bdc = 1,4-benzenedicarboxylic acid) have been synthesized under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses, and further characterized by infrared spectra (IR), elemental analyses and powder X-ray diffraction (PXRD). Compound 1 displays a two-dimensional (2D) layer structure, which is stabilized by intramolecular hydrogen-bonding interactions. Compounds 2 and 3 are isostructural and show 2D layer structures, which are further extended by intermolecular C-H···O hydrogen-bonding interactions to form 3D supramolecular frameworks. Compound 4 has a 2D layer structure with trinuclear units [Cd₃(u₃-O)₂]⁶⁺. Compound 5 is a 3D three-fold interpenetrating framework with a Schläfli symbol (6⁶·8). The structural differences of these compounds indicate that the anions play important roles in the resulting structures of the MOFs. The luminescent properties were also investigated for compounds 1-5.     

Three Functionalized Zinc(II)/Cobalt(II) Coordination Complexes Demonstrating Fluorescent Sensing Activities towards Fe3+ Ions and Photocatalytic Selectivity for Organic Dyes

Three new zinc(II)/cobalt(II) coordination complexes [Zn(HBTB)(L)_0.5] ( 1 ), [Zn(HCPPA)(L)] ( 2 ), and [Co(HCPPA)(L)] · 2H₂O ( 3 ) [H₃BTB = 1,3,5-tri(4-carboxylphenyl)benzene, H₃CPPA = 5-(4-carboxyl-phenoxy)-isophthalic acid, L = N¹,N⁴-bis(3-pyridyl)naphthaldiamide] were solvothermally synthesized. The structural characterization reveals that complex 1 represents a 3D coordination framework with a binodal 3,4-connected {4.10²}₂{4.10⁵}₂ topology constructed from the 2D [Zn(HBTB)]_n polymeric double-layers and the bidentate L ligands. Complex 2 is a 1D metal-organic chain derived from the dinuclear [Zn₂(HCPPA)₂] loops and [Zn₂(L)₂] loops. Complex 3 possesses a binodal 3,5-connected {4².6}{4³.6.8⁴.10²} topological 2D layered architecture based on the [Co₂(HCPPA)₂] ribbon chains and the bidentate L ligands. For 2 and 3 , their adjacent chains or layers are respectively stacked into 3D supramolecular architectures via the hydrogen bonds. Moreover, the fluorescent and fluorescent sensing activities towards small solvent molecules of coordination complexes 1 and 2 , the photocatalyitc properties of 1 – 3 towards organic dyes were studied.     

A series of silver coordination polymers constructed from flexible bis(benzimidazole) ligands and different carboxylates

In this article, eight new silver coordination polymers constructed from two structurally related ligands, 1,1′-(1,4-butanediyl)bis(2-methylbenzimidazole) (bbmb) and 1,1′-(1,4-butanediyl)bis(2-ethylbenzimedazole) (bbeb), have been synthesized: [Ag(L1)(bbmb)]·C₂H₅OH·H₂O (1), [Ag(L2)(bbmb)]·C₂H₅OH (2), [Ag(L3)(bbmb)] (3), [Ag₂(L4)(bbmb)₂]·C₂H₅OH (4), [Ag(L2)(bbeb)]·C₂H₅OH (5), [Ag(L5)(bbeb)]·CH₃OH (6), [Ag₂(L6)₂(bbeb)]·H₂O (7), and [Ag₂(L7)(bbeb)₂]·4(H₂O) (8), where L1 = benzoate anion, L2 = p-methoxybenzoate anion, L3 = 2-amino-benzoate anion, L4 = oxalate anion, L5 = cinnamate ainon, L6 = 3-amino-benzoate anion, and L7 = fumaric anion. In 1-3, 5 and 6, the bidentate N-donor ligands (bbmb and bbeb) in trans conformations bridge neighboring silver centers to form 1D single chain structures. The carboxylate anions are attached on both sides of the chains. Moreover, 1 and 3 are extended into 2D layers, while 2 and 6 are extended into 3D frameworks through π-π interactions. In 4, the bbmb ligands bridge adjacent Ag(I) centers to form -Ag-bbmb-Ag- chains, which are further connected by L4 anions to form a 2D layer. The resulting layers are extended into 3D frameworks through strong π-π interactions. In 7, the N-donor ligands (bbeb) in trans conformations bridge two silver centers to generate a [Ag₂(bbeb)]²⁺ unit. The adjacent [Ag₂(bbeb)]²⁺ units are further connected via the L6 anions to form a 1D ladder chain. Moreover, the structure of compound 7 is extended into a 3D framework through hydrogen bonding and π-π interactions. In 8, two Ag(I) cations are bridged by two bbeb ligands in cis conformations to form a [Ag₂(bbeb)₂]²⁺ ring, which are further linked by L7 anions to generate a 1D string chain. Furthermore, the hydrogen bonding and π-π interactions link L7 anions to form a 2D supramolecular sheet. Additionally, the luminescent properties of these compounds were also studied.     

Metal–organic frameworks (MOFs) constructed from Zn/Cd-2,2′-bipyridines and polycarboxylic acids: Synthesis,characterization and microstructural studies

Metal–organic frameworks with the compositions [Zn(bpy)(bdc)(H₂O)]_n1, [Zn(bpy)(btec)_1/2(H₂O)]_n2, [Cd(bpy)(bdc)(H₂O)]_n3 and Cd(bpy)(btec)_1/2(H₂O)]_n4 (H₂bdc = 1,4-benzenedicarboxylic acid = terephthalic acid, H₄btec = 1,2,4,5-benzenetetracarboxylic acid and bpy = 2,2′-bipyridine) have been synthesized and characterized using spectroscopic and single-crystal X-ray diffraction techniques. In these complexes, Zn^II/Cd^II-2,2′-bipyridine units and carboxylate anions exists as nodes and spacers respectively. An infinite 1D zig-zag chain structure is observed for both complexes 1 and 3, whereas complexes 2 and 4 display a 3D supramolecular architecture. The complexes are found to be photoluminescent, porous and show significant thermal stability.     

Urothermal Syntheses of two New Luminescent Zinc(II) Compounds via Dual-ligand Strategy

Urothermal reaction of Zn(NO₃)₂ · 6H₂O, Htrz and NH₂H₂pdc or H₂pdc affords two new compounds, namely [Zn₂(NH₂bdc)(trz)₂]_n · 2n(e-urea) ( 1 ) and [Zn₄(bdc)₂(trz)₄(H₂O)(e-urea)]_n · n(e-urea) ( 2 ) (Htrz = 1,2,4-triazole, NH₂H₂bdc = 2-aminoterephthalic acid, H₂bdc = terephthalic acid, e-urea = 1,3-ethyleneurea). X-ray structural analyses revealed that both compounds 1 and 2 feature e-urea-templated 3D pillar-layer framework with 2D Zn^II-triazole layer and 6-connected pcu topological network. These two compounds not only have high thermal stabilities but also show intense luminescence at room temperature.     

Structural variation from linear,layer to 3D framework: Syntheses,structures and luminescence

Self‐assembly of Zn (II) or Cd (II) nitrates, flexible bis (pyridyl)‐diamine, as well as arenesulfonic acids, leads to the formation of ten coordination polymers, namely, [Zn(L1)(H₂O)₃]·2(p‐TS)·2H₂O ( 1 ), [Zn(L1)(H₂O)₂]·2(p‐TS)·2H₂O ( 2 ), [Zn(L1)₂(p‐TS)₂] ( 3 ), [Zn(H₂L1)(H₂O)₄]·2(1,5‐NDS)·2H₂O ( 4 ), [Zn(H₂L2)(H₂O)₄]·2(1,5‐NDS)·4MeOH ( 5 ), [Cd(L1)(p‐TS)(NO₃)]·H₂O ( 6 ), [Cd(L1)(1,5 ‐NDS)_0.5(H₂O)]·0.5(1,5‐NDS)·H₂O ( 7 ), [Cd(L2)(H₂O)₂]·(p‐TS)·(NO₃)·3H₂O ( 8 ), [Cd(L2)(1,5‐NDS)] ( 9 ) and [Cd(L2)(1,5‐NDS)]·MeOH ( 10 ) (L1 = N,N′‐bis (pyridin‐4‐ylmethyl) ethane‐1,2‐diamine, L2 = N,N′‐bis (pyridin‐3‐ylmethy l)ethane‐1,2‐diamine, p‐HTS = p‐toluenesulfonic acid, 1,5‐H₂NDS = 1,5‐naphthalene disulfonic acid), which have been characterized by elemental analysis, IR, TG, PL, powder and single‐crystal X‐ray diffraction. Complexes 1 , 4 , 5 and 6 present linear or zigzag chain structures accomplished by the interconnection of adjacent M (II) cations through L1 ligands or protonated H₂L1²⁺/H₂L2²⁺ cations, while complexes 2 , 3 and 8 show similar (4,4) layer motifs constructed from the connection of M (II) cations through L1 and L2. The same coordination modes of L1 and L2 in complexes 7 and 9 join adjacent Cd (II) cations to form double chain structures, which are further connected by bis‐monodentate 1,5‐NDS^2? dianions into different (6,3) and (4,4) layer motifs. The L2 molecules in complex 10 join adjacent Cd (II) cations together with 1,5‐NDS^2? dianions to form 3D network with hxl topology. Therefore, the diverse coordination modes of the bis (pyridyl) ligand with chelating spacer and the feature of different arenesulfonate anions can effectively influence the architectures of these complexes. Luminescent investigation reveals that the emission maximum of these complexes varies from 374 to 448 nm in the solid state at room temperature, in which complexes 4 , 5 , 7 , 9 and 10 show average luminescence lifetimes from 7.20 to 14.82 ns. Moreover, photocatalytic properties of complexes 7–10 towards Methylene blue under Xe lamp irradiation are also discussed.     

基于半刚性双(噻唑基苯并咪唑)和不同羧酸的五个一维配合物的合成和表征

通过水热或溶剂热合成的方法制备了5个一维配合物{[Zn(btbb)_(0.5)(m-phda)]·0.5H_2O}_n(1),{[Cd_2(btbb)(adtda)_2(H_2O)]·H_2O}_n(2),[Mn_2(btbb)(tbi)_2]_n(3),{[Cd(btbb)_(0.5)(3-Nitro-o-bdc)(H_2O)]·H_2O}_n(4)和[Cd_2(btbb)(tbi)_2]_n(5)(btbb=1,4-双(2-(4-噻唑基)苯并咪唑-1-基甲基)苯,m-H_2phda=间苯二甲酸,H_2adtda=1,3-金刚烷二羧酸,H_2tbi=5-叔丁基间苯二甲酸,3-Nitro-o-H_2bdc=3-硝基-1,2-苯二甲酸)。配合物1是一个包含22元环的一维链。配合物2是一个包含8元环的一维链,并且氮配体在这个一维链中仅仅起到装饰作用。配合物3是一个一维双链结构。配合物4是一个包含14元环的一维链。配合物5是一个阶梯状的一维双链结构。     

Controlling the BET Surface Area of Porous Carbon by Using the Cd/C Ratio of a Cd–MOF Precursor and Enhancing the Capacitance by Activation with KOH

Herein, four new cadmium metal–organic frameworks (Cd–MOFs), [Cd(bib)(bdc)]_∞ ( 1 ), [Cd(bbib)(bdc)(H₂O)]_∞ ( 2 ), [Cd(bibp)(bdc)]_∞ ( 3 ), and [Cd₂(bbibp)₂(bdc)₂(H₂O)]_∞ ( 4 ), have been constructed from the reaction of Cd(NO₃)₂ ? 4 H₂O with 1,4‐benzenedicarboxylate (H₂bdc) and structure‐related bis(imidazole) ligands (1,4‐bis(imidazol‐1‐yl)benzene (bib), 1,4‐bis(benzoimidazol‐1‐yl)benzene (bbib), 4,4′‐bis(imidazol‐1‐yl)biphenyl (bibp), and 4,4′‐bis(benzoimidazol‐1‐yl)biphenyl (bbibp)) under solvothermal conditions. Cd–MOF 1 shows a 2D (4,4) lattice with parallel interpenetration, whereas 2 displays an interesting 3D interpenetrating dia network, 3 exhibits an unusual 3D interpenetrating dmp network, and 4 presents a 3D self‐catenated pillar‐layered framework with a Schäfli symbol of [4³ ? 6³]₂ ? [4⁶ ? 6¹⁶ ? 8⁶]. The structural diversity indicates that the backbone of the bis(imidazole) ligand (including the terminal group and spacer) plays a crucial role in the assembly of mixed‐ligand frameworks. By using the pore‐forming effect of cadmium vapor, for the first time we have utilized these Cd–MOFs as precursors to further prepare porous carbon materials (PCs) in a calcination–thermolysis procedure. These PCs show different porous features that correspond to the topological structures of Cd–MOFs. Significantly, it was found that the specific surface area and capacitance of PCs are tuned by the Cd/C ratio of the MOF. Furthermore, the as‐synthesized PCs were processed with KOH to obtain activated porous carbon materials (APCs) with higher specific surface area and porosity, which greatly promoted the energy‐storage capacity. After full characterization, we found that APC‐bib displays the largest specific surface area (1290 m² g^?1) and total pore volume (1.37 cm³ g^?1) of this series of carbon materials. Consequently, APC‐bib demonstrates the highest specific capacitance of 164 F g^?1 at a current density of 0.5 A g^?1, and also excellent retention of capacitance (≈89.4 % after 5000 cycles at 1 A g^?1). Therefore, APC‐bib has great potential as the electrode material in a supercapacitor.     

Assembled synthesis of luminescent mono/double‐layered 2D and 3D Zn (II)‐based coordination polymers tuned by flexible bis (pyridyl)propane‐1,2‐diamines and diverse organic dicarboxylates

Six mono/double‐layered 2D and three 3D coordination polymers were synthesized by a self‐assembly reaction of Zn (II) salts, organic dicarboxylic acids and L1/L2 ligands. These polymeric formulas are named as [Zn(L1)(C₄H₂O₄)_0.5 (H₂O)]_n·0.5n(C₄H₂O₄)·2nH₂O ( 1 ), [Zn₂(L2)(C₄H₂O₄)₂]_n·2nH₂O ( 2 ), [Zn(L1)(m‐BDC)]_n ( 3 ), [Zn₂(L2)(m‐BDC)₂]_n·2nH₂O ( 4 ), [Zn₃(L1)₂(p‐BDC)₃(H₂O)₄]_n·2nH₂O ( 5 ), [Zn₂(OH)(L2) (p‐BDC)_1.5]_n ( 6 ), [Zn₂(L1)(p‐BDC)₂]_n·5nH₂O ( 7 ), [Zn₂(L2)(p‐BDC)₂]_n·3nH₂O ( 8 ) and [Zn₂(L1)(C₄H₄O₄)_1.5(H₂O)]_n·n(ClO₄)·nH₂O ( 9 ) [L1 = N,N′‐bis (pyridin‐4‐ylmethyl)propane‐1,2‐diamine, L2 = N,N′‐bis (pyridin‐3‐ylmethyl)propane‐1,2‐ diamine, m‐BDC^2? = m‐benzene dicarboxylate, p‐BDC^2? = p‐benzene dicarboxylate]. Meanwhile, these polymers have been characterized by elemental analysis, infrared, thermogravimetry (TG), photoluminescence, powder and single‐crystal X‐ray diffraction. Polymers 1–6 present mono‐ and double (4,4)‐layer motifs accomplished by L1/L2 ligands with diverse conformations and organic dicarboxylates, and the layer thickness locates in the range of 5.8–15.0 Å. In three 3D polymers, the L1 and L2 molecules adopt the same cis‐conformations and join adjacent Zn (II) cations together with p‐BDC^2? or succinate, giving rise to different binodal (4,4)‐c nets with (4.5².8³)(4.5³.7²) ( 7 ), pts ( 8 ) topology and twofold interpenetrated binodal (5,5)‐c nets with (3².4⁴.5².6²)(3.4³.5².6⁴) ( 9 ). Therefore, the diverse conformations of the two bis (pyridyl)‐propane‐1,2‐diamines and the feature of different organic dicarboxylate can effectively influence the architectures of these polymers. Powder X‐ray diffraction patterns demonstrate that these bulk solid polymers are pure phase. TG analyses indicate that these polymers have certain thermal stability. Luminescent investigation reveals that the emission maximum of these polymers varies from 402 to 449 nm in the solid state at room temperature. Moreover, 1 , 3 and 5–8 show average luminescence lifetimes from 8.81 to 16.30 ns.